Formation of CaCO₃ hollow microspheres in carbonated distiller waste from Solvay soda ash plants

Abstract

For decades, distiller waste and CO₂ were not the first choice for production of high valued products. Here, CaCO₃ hollow microspheres, a high-value product was synthesized from such a reaction system. The synthetic methods, the formation mechanism and operational cost were discussed. When 2.5 L·min^–1·L^–1 CO₂ was flowed into distiller waste (pH = 11.4), spheres with 4–13 μm diameters and about 2 μm shell thickness were obtained. It is found that there is a transformation of CaCO₃ particles from solid-cubic nuclei to hollow spheres. Firstly, the Ca(OH)₂ in the distiller waste stimulated the nucleation of calcite with a non-template effect and further maintained the calcite form and prevented the formation of vaterite. Therefore, in absence of auxiliaries, the formation of hollow structures mainly depended on the growth and aging of CaCO₃. Studies on the crystal morphology and its changes during the growth process point to the inside–out Ostwald effect in the formation of hollow spheres. Change in chemical properties of the bulk solution caused changes in interfacial tension and interfacial energy, which promoted the morphological transformation of CaCO₃ particles from cubic calcite to spherical clusters. Finally, the flow process for absorption of CO₂ by distiller waste was designed and found profitable.

Graphical abstract

Keywords

distiller waste / CO₂ / hollow microsphere / CaCO₃ / Ca(OH)₂ / inside−out Ostwald effect

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Acknowledgements

This work is supported by the National Natural Science Foundation of China (Grant Nos. U20A20149, 21878180 and 21908137) and the Graduate Education Project of Shanxi Province (NO. 2021Y139).

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://dx.doi.org/10.1007/s11705-022-2173-z and is accessible for authorized users.

Nomenclature

XV	the molar fractions of vaterite
XC	the molar fractions of calcite
Ic104	104 crystal plane peak intensities of calcite
Iv110	110 crystal plane peak intensities of vaterite
V_{{\mathrm{C}\mathrm{O}}_2}	the total amount of CO2 consumed during the carbonation reaction for 1 h, L
V	the volume of solution, L
Vm	the standard molar volume of a gas, L·mol–1
n_{{\mathrm{C}\mathrm{a}\left(\mathrm{O}\mathrm{H}\right)}_2}	the amount of insoluble Ca(OH)2 reacted part at time t (negligible), mol
M	molecular weight of Ca(OH)2, g·mol–1
n	the amount of undissolved Ca(OH)2, mol
c_{{\mathrm{C}\mathrm{a}}_0^{2+}}	the initial concentration of Ca2+ in the solution, mol·L–1
c_{{\mathrm{C}\mathrm{a}}_t^{2+}}	the concentration of Ca2+ in the solution at time t, mol·L–1
c_{{\mathrm{C}\mathrm{a}}^{2+}}	the concentration of Ca2+, mol·L–1
c_{{\mathrm{O}\mathrm{H}}^{-}}	the concentration of OH–, mol·L–1
J	the activity products
K	solubility product constant of Ca(OH)2, K = 5.6 × 10−6 (25 °C)
{\gamma }_{{\mathrm{C}\mathrm{a}}^{2+}}	the activity coefficients of Ca2+
{\gamma }_{{\mathrm{O}\mathrm{H}}^{-}}	the activity coefficients of OH–
{\alpha }_{{\mathrm{C}\mathrm{a}}^{2+}}	activity of Ca2+ in solution, mol·L–1
{\alpha }_{{\mathrm{O}\mathrm{H}}^{-}}	activity of OH− in solution, mol·L–1
\theta	contact angle between calcite and liquid, (°)
{\gamma }_{\mathrm{l}\mathrm{s}}	solid–liquid interfacial tension, mN·m–1
{\gamma }_{\mathrm{l}\mathrm{g}}	liquid–vapor interfacial tension, mN·m–1
{\gamma }_{\mathrm{s}\mathrm{g}}	solid–vapor interfacial tension, mN·m–1, {\gamma }_{\mathrm{s}\mathrm{g}}= 43.5 mN·m–1
c_{{\mathrm{C}\mathrm{a}}_{20\mathrm{m}\mathrm{i}\mathrm{n}}^{2+}}	the concentration of Ca2+ in the system reacted for 20 min, mol·L–1
Y	the output of CaCO3 hollow microspheres, kg
T	cycle times of carbonation of distiller waste
V'	the volume of distiller waste, L
M'	the molecular weight of CaCO3, g·mol–1

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